C-F bond activation in polyfluorobenzothiolate compounds of os(III)

Article abstract of DOI:10.1016/S0022-328X(99)00760-3

Thermolysis of [Os(SR)₃(PMe₂Ph)₂] (R = C₆F₅ (1a) or C₆HF₄-4 (1b)) in refluxing toluene affords [Os(SC₆F₅)₂-(o-S₂C₆F₄)(PMe₂Ph)] (2a), [Os(SC₆HF₄)₂(o-S₂C₆HF₃)(PMe₂Ph)] (2b), and [Os(C₆F₅)₂(o-S₂C₆F₄)(PMe₂Ph)₂] (3a) through processes involving C-F and C-S bond cleavage as well as rearrangement of C-S bonds. The single-crystal diffraction structures of 1a, 2a and 3a have been determined. In the solid state compound 1a shows a C-F→Os interaction.

Full text of DOI:10.1016/S0022-328X(99)00760-3

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 599 (2000) 170–177
CꢀF bond activation in polyfluorobenzothiolate compounds of
¸¹¹¹¹º
Os(III). X-ray structures of [Os(SC6F4(F-2))(SC6F5)2(PMe2Ph)2],
[Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] and
[Os(C6F5)2(o-S2C6F4)(PMe2Ph)2]
Maribel Arroyo a, Sylvain Berne`s b, Jose Luis Brianso c, Estela Mayoral b,
Raymond L. Richards d, Jordi Rius e, Hugo Torrens b,*
a Centro de Qu´ımica, Instituto de Ciencias, BUAP, Boule6ard 14 Sur 6303, Cd. Uni6ersitaria, 72570 Puebla, Puebla, Mexico
b DEPg., F. de Qu´ımica, Cd. Uni6ersitaria, 04510 Mexico D.F., Mexico
c Unidad de Cristalografia, F. de Ciencias, UAB, E-08193 Bellaterra, Spain
d John Innes Centre, Norwich Research Park, Colney, Norwich NR4 7UH, UK
e Institut de Ciencia de Materials de Barcelona, Campus de la UAB, E-08193 Bellaterra, Spain
Received 7 April 1999; received in revised form 9 December 1999
Abstract
Thermolysis of [Os(SR)3(PMe2Ph)2] (R=C6F5 (1a) or C6HF4-4 (1b)) in refluxing toluene affords [Os(SC6F5)2-
(o-S2C6F4)(PMe2Ph)] (2a), [Os(SC6HF4)2(o-S2C6HF3)(PMe2Ph)] (2b), and [Os(C6F5)2(o-S2C6F4)(PMe2Ph)2] (3a) through processes
involving CꢀF and CꢀS bond cleavage as well as rearrangement of CꢀS bonds. The single-crystal diffraction structures of 1a, 2a
and 3a have been determined. In the solid state compound 1a shows a CꢀF“Os interaction. © 2000 Elsevier Science S.A. All
rights reserved.
Keywords: C–F bond activation; Polyfluorobenzothiolate; Osmium; Thermolysis
We have now found that thermolysis of
[Os(SR)3(PMe2Ph)2] (R=C6F5 (1a) or C6HF4-4 (1b)) in
1. Introduction
refluxing toluene causes a substantial rearrangement–
The activation of fluorinated hydrocarbons by metal
oxidative reaction giving rise to a complex mixture of
centres has been an area of intense study during the last
products from which the Os(IV) complexes
decade [1–9]. Structural reports of transition-metal
[Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] (2a), [Os(SC6HF4-
complexes with carbon–fluorine–metal interactions
4)2(o-S2C6HF3)(PMe2Ph)] (2b) and [Os(C6F5)2(o-
[10,11] as well as research focused on carbonꢀfluorine
S2C6F4)(PMe2Ph)2]
(3a)
have
been
isolated.
bond activation [12–14] have been reviewed recently.
Previously, we have reported the synthesis of
[M(SC6F5)3(PMe2Ph)2] (M=Ru, Os) and the X-ray
structure of the ruthenium compound, showing that
this complex bears a CꢀFꢀRu interaction in the solid
state [15,16]. The X-ray structure of the osmium com-
pound has also been published as a preliminary report
[17].
Compounds 1a, 2a and 3a, have been structurally
characterised.
2. Results and discussion
The synthesis of the formally pentaco-ordinated,
Os(III) d5 complexes [Os(SR)3(PMe2Ph)2] (R=C6F5
(1a) or C6HF4-4 (1b)) has been previously reported
[15,16]. Since [Ru(SC6F5)3(PMe2Ph)2] has been shown
to have a RuꢀFꢀC interaction, we carried out an X-ray
diffraction molecular structure determination of
* Corresponding author. Fax: +52-5-6223724.
E-mail address: torrens@servidor.unam.mx (H. Torrens)
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00760-3

M. Arroyo et al. / Journal of Organometallic Chemistry 599 (2000) 170–177
171
A further feature of this structure is that the C6F5
groups attached to S(3) and S(5) are eclipsed about the
S···S vector; they are thus aligned with the central
chelating ligand to form, as closely as possible, a stacked
pattern.
In exploring the reactivity of compounds 1a–b we
have found that in refluxing dry toluene under nitrogen,
[Os(SR)3(PMe2Ph)2] (R=C6F5 (1a) or C6HF4-4 (1b)) is
involved in thermolysis reactions. The original dark pur-
ple solutions slowly turn green and the chromatographic
resolution of the final mixtures gives rise to two, from
1a, or one, from 1b, distinct, highly coloured fractions.
Additionally, GLC–mass spectrometry analyses of
the solvent indicate the presence of C6HF5 and C6H2F4
from the reactions of 1a and 1b, respectively. As dis-
cussed below, three of the reaction products have been
identified according to the following reactions:
[Os(SC6F5)3(PMe2Ph)2] (1a) in a search for a similar
bond. The molecular structure of 1a is shown in Fig. 1,
and selected bond distances and angles are collected in
Table 1.
The important feature of this structure is the interac-
tion of an ortho-fluorine of one of the SC6F5 ligands
with the metal to create an SꢀF chelate ligand, thus
achieving six coordination in an approximately octahe-
,
dral arrangement. The OsꢀF distance of 2.531(6) A is
shorter than the calculated van der Waals distance
,
[18,19] (3.1 A) and implies a moderate bond strength of
this three-centre, four-electron CꢀFꢀOs bond.
Metalꢀfluorine distances in CꢀFꢀM bonds span from
,
2.15 to 3.30 A, between 24 and 8% shorter than the sum
of fluorine and metal van der Waals radii
,
[10,11]. Therefore, the OsꢀF distance of 2.531(6) A
found in 1a lies at the lower end of this scale and it is al-
most 19% shorter than the corresponding van der Waals
distance.
[Os(SC6F5)3(PMe2Ph)2] (1a)
“[Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] (2a)
+[Os(C6F5)2(o-S2C6F4)(PMe2Ph)2] (3a)
[Os(SC6HF4-4)3(PMe2Ph)2] (1b)
“[Os(SC6HF4-4)2(o-S2C6HF3)(PMe2Ph)] (2b)
Complexes [Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] (2a) and
[Os(SC6HF4)2(o-S2C6HF3)(PMe2Ph)] (2b) are dark
green, crystalline solids. The FAB mass spectra of both
compounds show the corresponding parent ions (2a m/
z=940, 68%; 2b m/z=886, 92%) from which successive
losses of SC6F5 and C6HF5 or SC6HF4-4 and C6H2F4
(2a m/z=741, 22% and 573, 12%; 2b m/z=705, 44%
and 555, 16%) are observed. The loss of C6F5 or C6HF4-
4 from the parent ions is also observed. A common sig-
nal in both spectra is that corresponding to
PMe2Ph+.
2.1. Crystal structure of
[Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] (2a)
Fig. 1. Structure of [Os(SC6F4(F-2))(SC6F5)2(PMe2Ph)2] (1a). (Ellip-
soids at 30% probability levels. Hydrogen atoms were omitted for
clarity.)
The
molecular
structure
of
[Os(SC6F5)2-
(o-S2C6F4)(PMe2Ph)] (2a) is shown in Fig. 2 and selected
bond distances and angles are collected in Table 2.
The structure of 2a shows an essentially trigonal-
bipyramidal coordination geometry with an axial
PMe2Ph group. The quelating dithiolate ligand occu-
pies both axial and equatorial positions with two equa-
torial (SC6F5)− moieties. The structure of 2a resembles
those of [OsCl(SC6F5)3(PMe2Ph)] [20], [Os(SC6HF4-
Table 1
,
Bond lengths (A) and angles (°) of [Os(SC6F5)3(PMe2Ph)2] (1a)
Distances
Angles
Os-P1
2.352(2)
2.274(2)
2.327(2)
2.415(2)
2.531(5)
2.328(2)
1.769(9)
1.765(8)
1.795(8)
S4ꢀOsꢀF42
S5ꢀOsꢀF42
S3ꢀOsꢀF42
P2ꢀOsꢀF42
P1ꢀOsꢀF42
P2ꢀOsꢀS3
S3ꢀOsꢀS5
P1ꢀOsꢀS4
P1ꢀOsꢀP2
76.36(11)
86.31(13)
83.53(13)
170.86(11)
94.45(11)
97.33(8)
165.55(8)
170.81(7)
94.69(8)
OsꢀP2
OsꢀS3
OsꢀS4
OsꢀF42
OsꢀS5
S3ꢀC31
S4ꢀC41
S5ꢀC51
4)4(PPh3)]
[21]
and
[OsCl(SC6F5)2(SC6H4(CF3)-
3)(PMe2Ph)] [21]. As might be expected [22], the axial
,
OsꢀS distance (2.381(3) A) is longer than the mean
,
equatorial OsꢀS distance (2.207(3) A). The angles
around the sulphur atoms show considerable varia-
tions, thus one thiolate shows a substantial distortion

172
M. Arroyo et al. / Journal of Organometallic Chemistry 599 (2000) 170–177
pound 2a, Fig. 3, showed three signals (A2BC2 mag-
netic system, intensities 4:2:4) corresponding to the
ortho-, para-and meta-fluorine nuclei of two magneti-
cally equivalent (SC6F5)− substituents and four addi-
tional absorptions (Intensities 1:1:1:1) arising from each
of the four distinct fluorine nuclei at the (S2C6F4)2−
moiety (ABCD magnetic system). As the temperature is
decreased, the ortho and meta signals from the thiolate
groups broaden (ca. 40°C) and eventually collapse (ca
20oC) giving rise, each one, to a pair of signals with the
same intensity which at lower temperatures (ca.
−40°C) reach their maximum definition without fur-
ther changes. It is important to notice that the para
signal remains unaffected during the process.
Except for small variations due to subtle changes in
magnetic couplings, the sub-spectra arising from the
dithiolate fragment remains essentially unchanged
through the full range of temperatures.
Fig. 2. Structure of [Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] (2a). (Ellipsoids
As suggested by the results from NMR experiments,
the fluxional behaviour of these complexes can be at-
tributed to a restricted CꢀS(thiolate) bond rotation on
this geometry.
at 30% probability levels. Hydrogen atoms were omitted for clarity.)
Table 2
,
Bond lengths (A) and angles (°) of [Os(SC6F5)2(o-S2C6F4)(PMe2Ph)]
(2a)
Although a completely equivalent set of 19F-NMR
results
is
obtained
when
[Os(SC6HF4-4)2(o-
Distances
Angle
S2C6HF3)(PMe2Ph)] (2b) is examined for fluxionality,
indicating also that the SꢀC6HF4-4 bonds are not free
to rotate, the 19F-NMR data show that [Os(SC6HF4-
4)2(o-S2C6HF3)(PMe2Ph)] exists as the pair of structural
isomers shown below:
OsꢀS20
OsꢀS30
OsꢀS40
OsꢀS50
OsꢀP10
P10ꢀC11
S20ꢀC21
S30ꢀC31
S40ꢀC41
S50ꢀC46
2.207(3)
2.213(3)
2.200(3)
2.381(3)
2.374(4)
1.823(7)
1.765(11)
1.761(11)
1.740(12)
1.749(11)
S40ꢀOsꢀS20
S40ꢀOsꢀS30
S30ꢀOsꢀS20
S40ꢀOsꢀS50
S20ꢀOsꢀS50
S30ꢀOsꢀS50
S20ꢀOsꢀP10
S30ꢀOsꢀP10
S40ꢀOsꢀP10
S50ꢀOsꢀP10
121.10(13)
118.84(13)
119.40(13)
87.76(12)
94.11(12)
96.27(13)
87.27(12)
87.75(13)
86.88(13)
174.40(13)
towards planarity, ꢀC(21)ꢀS(20)ꢀOs 116.2(4)°, when
compared to the second thiolate, ꢀC(31)ꢀS(30)ꢀOs
111.7(4)°. At the dithiolate ligand, both these angles are
closer to tetrahedral rather than to planar,
ꢀC(41)ꢀS(40)ꢀOs
107.8(5)°
and
C(46)ꢀS(50)ꢀOs
Both isomers differ in the relative position of the
hydrogen atom at the dithiolate ring either attached to
carbon 4 or carbon 5 relative to the axial sulfur atoms.
At room temperature both isomers are present with a
proportion of 4 to 1 (H-C4 to H-C5, respectively).
As expected, 31P-NMR spectra of compounds 2a and
2b exhibit multiplets due to P(CH3)2 coupling (see Fig.
4). However, 31P-{1H}-NMR spectra show one doublet
for compound 2a and one doublet for each of the two
isomers of compound 2b. Two-dimensional HETCOR
31P-19F-NMR experiments indicate a relatively long-
range ‘trans’ phosphorus–fluorine magnetic coupling
102.5(5)°. The tendency towards planarity around sul-
fur atoms has been previously associated with a sub-
stantial contribution to metal-sulfur p-bonding
discouraging inversion of configuration and free metal-
sulfur bond rotation [23].
On the other hand, there is no significant difference
in equatorial OsꢀS distances from S-thiolate and S-
dithiolate ligands.
The dithiolate ligand (S2C6F4)2− forms a five-mem-
bered quelated ring with the osmium atom and the
plane defined by the OsS(40)S(50)C6F4 moiety is the
plane bisecting the S20ꢀOsꢀS30 angle.
5
5
Variable-temperature 19F-NMR of compounds 2a
and 2b shows these molecules to be fluxional. At high
temperature (ca. 80°C) the 19F-NMR spectra of com-
with JPꢀF=8Hz, S2C6F4 (2a), JPꢀF=7.8Hz, S2C6F3H-
4 (2b, isomer A) and 5JPꢀF=7.8Hz, S2C6F3H-5 (2b,
isomer B). See Fig. 4.

M. Arroyo et al. / Journal of Organometallic Chemistry 599 (2000) 170–177
173
Fig. 3. Variable-temperature 19F-NMR of [Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] (2a). Signals a from SC6F−5 , signals b from S2C6F24−
.
Apparently, as a result of mesomeric effects, the
exchange of positions between HꢀC4 and HꢀC5 in
isomers A and B inverts the relative chemical-shift
order of the fluorine nuclei. Thus, for isomer A, lF3
and lF5 are larger than lF6, whereas for isomer B,
lF6 is larger than lF4 and lF3.
2.2. Crystal structure of
[Os(C6F5)2(o-S2C6F4)(PMe2Ph)2] (3a)
The
molecular
structure
of
[Os(SC6F5)2(o-
S2C6F4)(PMe2Ph)2] is shown in Fig. 5 and selected bond
distances and angles are collected in Table 3.
The activation energies for rotation about the SꢀC6F5
in 2a and SꢀC6HF4-4 in 2b are the same within experi-
mental error. These DGA are calculated to be 58.8594
kJ mol−1, slightly higher than those found for PꢀC6F5
[24].
The complex [Os(C6F5)2(o-S2C6F4)(PMe2Ph)2] (3a) is
a red crystalline solid. The FAB mass spectrum of this
compound shows the corresponding parent ion from
which successive losses of C6F5 and PMe2Ph follow.
The structure of 3a shows an essentially octahedral
coordination geometry with trans phosphine ligands
(P(20)ꢀOsꢀP(30) 176.74(8)°). The quelating dithiolate
ligand displays an angle of S(17)ꢀOsꢀS(10) 86.63(8)°.
The angles around the sulfur atoms OsꢀS(10)ꢀC(11)
105.52(25), OsꢀS(17)ꢀC(16), 106.93(25) suggest that the
dithiolate sulfur atoms are nearly tetrahedral (109°).
Room-temperature 19F-NMR spectra of compound
[Os(C6F5)2(o-S2C6F4)(PMe2Ph)2] (3a) show seven

174
M. Arroyo et al. / Journal of Organometallic Chemistry 599 (2000) 170–177
Fig. 4. HETCOR 31P-19F-NMR experiments of (a) [Os(SC6F4H-4)2(o-S2C6HF3)(PMe2Ph)2] (2b) and (b) [Os(SC6F5)2(o-S2C6F4)(PMe2Ph)2] (2a) (in
C6D6).
equally intense resonances corresponding to the seven
distinct fluorine atoms as found on the solid-state struc-
ture. Two of these signals arise from fluorine atoms at
the dithiolate ligand and five additional signals arise
from two C6F5 rings, each ring bearing distinct ortho-
and meta-fluorine substituents.
4)2(o-S2C6HF3)(PMe2Ph)] (2b) from the thermolysis of
[Os(SC6F5)3(PMe2Ph)2] or [Os(SC6HF4-4)3(PMe2Ph)2],
involves phosphine dissociation, cleavage of an ortho-
carbonꢀfluorine bond at a thiolate ligand, transfer of a
sulfur atom (and therefore carbonꢀsulfur bond splitting)
and oxidation of the metal centre.
A CꢀFꢀOs interaction is expected to induce an acti-
vated ortho-CꢀF bond, bearing an electrophilic carbon
atom. Such interactions are known to render CꢀF bonds
highly susceptible to nucleophilic attack. Therefore the
ortho-carbon atom can be envisaged as the centre of
such a nucleophilic reaction with a thiolateꢀsulfur atom.
Nucleophilic displacement of ortho-fluorine from pe-
rfluorinated aromatic ligands attached to transition
metals has been observed in a few examples where the
C6F5 ring is bound to carbon or phosphorus atoms
Variable-temperature 19F-NMR spectra of 3a show
no signs of fluxionality for this molecule from −30 to
50°C. These results suggest that the C6F5 rings remain
rigid, as found in the solid-state structure, probably
because the relatively large PMe2Ph ligands hinder the
OsꢀC free rotation. As expected, the 31P-{1H}-NMR
spectra of 3a at room temperature show a single
resonance.
The
formation
of
the
Os(IV)
complexes
[Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] (2a) or [Os(SC6HF4-

M. Arroyo et al. / Journal of Organometallic Chemistry 599 (2000) 170–177
175
(Merck, 5×7.5 cm2 Kiesegel 60 F254) was used when
possible to monitor the progress of the reaction under
study.
Complexes were characterised by IR spectra recorded
over the 4000–200 cm−1 range on a Perkin–Elmer
FTIR-1600, as CsI pellets.
1H-, 19F-, 31P-{1H} and HETCOR 19F-31P-NMR
spectra were measured with a SDS-360 MHz and a
modified NT-360 spectrometer operating at 360, 338
and 145 MHz, respectively by Spectral Data Services
Inc. (IL, USA); chemical shifts are relative to TMS
l=0 (1H), CFCl3 l=0 (19F) and H3PO4 l=0 (31P). A
standard variable-temperature unit was used to control
the probe and it was checked periodically by a thermo-
couple to ensure that the temperature readings were
within 91°C. Complexes were studied in C6D5CD3,
C6D6 and CDCl3.
Elemental analyses were determined by Galbraith
Labs., USA.
Fig. 5. Structure of [Os(C6F5)2(o-S2C6F4)(PMe2Ph)2] (3a), (Ellipsoids
at 30% probability levels. Hydrogen atoms were omitted for clarity.)
FAB spectra were obtained on a JEOL JMS SX102-
A mass spectrometer operated at an accelerating
voltage of 10 kV. Samples were desorbed from 3-ni-
trobenzyl alcohol matrix using 3keV xenon atoms.
Mass measurements in FAB are performed at 3000
resolution using magnetic field scans and the matrix
ions as the reference material, or electric field scans
with the sample peak bracketed by two (polyethylene
Table 3
,
Bond lengths (A) and angles (°) of [Os(C6F5)2(o-S2C6F4)(PMe2Ph)2]
(3a)
Distances
Angles
C40ꢀOs
C50ꢀOs
S17ꢀOs
2.170(7)
2.182(8)
2.281(2)
2.286(2)
2.428(2)
2.429(3)
1.734(9)
1.707(8)
1.394(7)
1.814(7)
1.829(5)
1.341(7)
P30ꢀOsꢀC40
P30ꢀOsꢀC50
P30ꢀOsꢀS17
P30ꢀOsꢀS10
P30ꢀOsꢀP20
OsꢀS10ꢀC11
OsꢀS17ꢀC16
S10ꢀOsꢀC40
S17ꢀOsꢀC50
S17ꢀOsꢀS10
C40ꢀOsꢀC50
S17ꢀOsꢀC40
S17ꢀOsꢀC50
S10ꢀOsꢀC50
86.15(21)
92.07(22)
86.11(9)
glycol
or
cesium
iodide)
reference
ions.
S10ꢀOs
97.51(9)
[Os(SR)3(PMe2Ph)2] (R=C6F5 (1a) or C6HF4 (1b))
were prepared according to the literature methods
[18,19].
P20ꢀOs
P30ꢀOs
S10ꢀC11
S17ꢀC16
C16ꢀC11
P30ꢀC31
P20ꢀC21
C42ꢀF42
176.74(8)
105.52(25)
106.93(25)
175.53(21)
175.59(22)
86.63(8)
92.81(28)
91.07(20)
175.59(22)
89.63(21)
3.1. Reaction of [Os(SC6F5)3(PMe2Ph)2] (1a)
[Os(SC6F5)3(PMe2Ph)2] (1a), (0.2 mmol), was dis-
solved in toluene (25 cm3). The deep purple solution
was kept under reflux for 9 h. The colour of the
solution slowly changed from purple to green. The
solvent was distilled off under vacuum. The solid
product was purified trough a chromatographic column
eluted with 10:1 hexane–dichloromethane. Two frac-
tions were separated and dried under vacuum at room
temperature for 4 h. Analyses and yield are as follow:
2a, yield 20%; green, m.p. 200–204°C, decomposes,
Anal. Calc.(%): C, 33.3; H, 1.2; S, 13.7: Found: C, 33.2;
[25–27]. On the other hand, migration of a C6F5 group
from a phosphine to Ir [28] and from a thiolate to Rh
[29] has been reported.
The mechanism of these reactions has not been estab-
lished but, since the products bear ortho-tetrafluoroben-
zene-dithiolate or ortho-trifluorobenzene-dithiolate
ligands, one of the original thiolate moieties had to be
involved in a reaction such that an ortho-fluorine atom
is replaced by sulfur.
1
H, 1.1; S, 13.8. H-RT-NMR, CDCl3, phosphine, l=
7.96, m, 2H, PPh; l=7.58, m, 3H, PPh; l=2.62, d,
6H, PCH3; 2JHꢀP=9.8 Hz. 19F-RT-NMR, C6D5CD3,
thiolate, l= −133.00, br m, 2Fo; l= −135.2, br m,
2Fo; l= −152.12, br t, 2Fp; l= −161.90, br m, 2Fm;
3
l= −162.7, br m, 2Fm; Jmꢀp=20.96 Hz; dithiolate,
3. Experimental
l= −136.91, pq, 1Fo; l= −139.30, dd, 1F; l= −
157.32, t, 1F; l= −163.02, t, 1F; 3JF3ꢀF4=22.2,
All manipulations were carried out under dry oxy-
gen-free dinitrogen atmospheres using Schlenk-tube
techniques. Toluene was dried and degassed using stan-
dard techniques; thin-layer chromatography (TLC)
4JF3ꢀF5=12.1,
3JF4ꢀF5=21.45,
4JF4ꢀF6=10.64,
3JF5ꢀF6=21.11 Hz. 31P-RT-NMR, C6D5CD3, l= −
5
20.31, d; JPꢀF6=8.76 Hz.

176
M. Arroyo et al. / Journal of Organometallic Chemistry 599 (2000) 170–177
3.2. Compound 3a
significant features were observed on the last difference
map (largest peak: 0.81 e A−3).
,
Yield 17%; red, m.p. 160–170°C, Anal. Calc.: C,
40.3; H, 2.2; S, 6.3; Found: C, 40.2; H, 2.1; S, 5.6%.
19F-RT-NMR, CD3COCD3, l= −143.7, m, 2F; l=
−160.48, t, 2F; l= −161.13, m, 2F; l= −164.07, t,
2F; l= −164.83, t, 2F; l= −177.52, d, 2F; l= −
190.0, d, 2F. 31P-RT-NMR, CD3COCD3, l=41.5, s.
The anisotropic refinement was performed without
constraints or restraints for 497 parameters and con-
verged at R1=0.0402% for 3496 data having F\4|(F)
and wR2=0.103% for all data with w=[|2(Fo2)+
(0.0511P)2+0.00P]−1, P=(max [Fo2,0]+2Fc2)/3, S=
1.067.
3.3. Reaction of [Os(SC6HF4)3(PMe2Ph)2] (1b)
3.5. [Os(SC6F5)2(o-S2C6F4)(PMe2Ph)] (2a)
As described above, yielding 2b after refluxing for 48
h, yield 17%; green, m.p. 205–210°C, decompose. Anal.
Calc.: C, 35.3; H, 1.6; S, 14.5; Found: C, 35.6; H, 1.6;
C26H11F14OsPS4, M=938.76 monoclinic, space
group P21/n, a=10.954(4), b=24.302(8), c=11.794(6)
3
,
,
A, h=90, i=110.95(3) k=90°, U=2932(2) A , Z=
1
S, 14.4%. H-RT-NMR, CDCl3, isomer A, phosphine,
4, T=293(2) K, Dc=2.127 g cm−3, F(000)=1792,
v(Mo–Ka)=4.797 mm−1, u(Mo–Ka)=0.71069 A.
,
l=7.99, m, 8H, PPh; l=7.58, m, 12H, PPh; l=2.62,
d, 24H, PCH3, l=6.81, m, 4H, dithiolate; l=7.01, m,
The crystals are deep green. Intensity data were col-
lected for a crystal of dimensions 0.20×0.10×0.05
mm mounted on a CAD4 diffractometer ꢀ/1.66q mode
with ꢀ scan width=0.80+0.34 tan q, ꢀ scan speed
1.3–5.5° min−1, graphite-monochromated Mo–Ka ra-
diation. Of 3194 reflections collected, 3014 were inde-
pendent. „-Scan absorption correction (max. and min.
transmission: 99.9 and 74.3) giving 1517 with I\2|(I).
q range for data collection: 2.16 to 21.00°, index ranges:
05h513, 05k530, −145l513. The structure was
solved by direct methods [31] (most atoms) followed by
difference Fourier synthesis and refined by full-matrix
least-squares on F2, using the SHELXL-93 program [30]
with all non-hydrogen atoms anisotropic. The weight-
ing scheme w=[|2(F2o)+(0.0000P)2+0.00P]−1 where
P=(Max[F2o]+2F2c)/3. Final R indices with I\2|(I):
R1=0.0399, wR2=0.0531, and R indices, with all data
R1=0.1473, wR2=0.0684.
2
8H, thiolate; JHꢀP=9.8 Hz; isomer B, phosphine, l=
7.99, m, 2H, PPh; l=7.58, m, 3H, PPh; l=2.64, d,
6H, PCH3; l=6.81, m, 1H, dithiolate; l=7.01, m, 4H,
thiolate; 2JHꢀP=9.6 Hz, 19F-RT-NMR, C6D5CD3,
numbering as in diagram 1, isomer A, dithiolate, l=
−114.94, pt, 0.8F6; l= −138.24, dd, 0.8F3; l= −
3
4
142.08, br m, 0.8F5; JF5ꢀF6=21.0, JF3ꢀF5=9.54 Hz;
thiolate, l= −133.84, br m, 2Fo; l= −135.63, br m,
2Fo; l= −139.15, br m, 2Fm; l=-140.04, br m, 2Fm;
isomer B, dithiolate, l= −111.78, m, 0.2F6; l= −
142.9, m, 0.2 F3; l= −144.5, dd, 0.2F4; thiolate,
l= −133.84, br m, 2Fo; l= −135.63, br m, 2Fo;
l= −139.15, br m, 2Fm; l= −140.04, br m, 2Fm.
31P-RT-NMR, C6D5CD3, isomer A, l= −20.14, br m,
5
4P; JPꢀF=7.8 Hz; isomer B, l= −20.58, br m, 1P;
5JPꢀF=7.8 Hz.
¸¹¹¹¹º
3.4. Crystal data: [Os(SC6F4(F-2))(SC6F5)2(PMe2Ph)2]
(1a)
3.6. [Os(C6F5)2(o-S2C6F4)(PMe2Ph)2] (3a)
C34H22F15OsP2S3, M=1063.8, orthorhombic, space
C34H22F14OsP2S2, M=1012.77, monoclinic, space
group P21/a, a=16.2965(10), b=12.1332(10), c=
group Pbca, a=18.142(3), b=18.064(2), c=22.954(3)
3
,
,
,
A, U=7522.5(19) A , Z=8, T=293(2) K, Dc=1.879
18.854(3) A, h=90, i=105.36(3), k=90°, U=
3
−3
,
g
cm−3
,
F(000)=4120, v(Mo–Ka)=3.74 mm−1
,
3594.8(7) A , Z=4, T=293(2) K, Dc=1.871 g cm
,
u(Mo–Ka)=0.71073 A. The crystals are deep blue
regular prisms. Intensity data were collected for a crys-
tal of dimensions 0.40×0.35×0.15 mm mounted on a
Siemens P4 diffractometer using Mo–Ka radiation.
One octant including redundant data was collected to
qmax=23° in a q/2q scan mode at variable speed,
between 3 and 60° min−1 (−15h519, −15k519,
−255l51, 6327 reflections). Lorentz polarisation and
absorption corrections were applied (42 „-scans, trans-
mission factors in the range 0.188–0.350), yielding 5200
unique reflections (Rint=4.24%). The structure was
solved from a Patterson map interpretation and refined
by full-matrix least-squares on F2 using the SHELXTL-93
program [30]. Hydrogen atoms were included on ide-
alised positions and refined using a riding model. No
F(000)=1960, v(Mo–Ka)=3.851 mm−1
,
u(Mo–
,
,
Ka)=0.71069 A. The crystals are red. Intensity data
were collected for a crystal of dimensions 0.39×0.12×
0.10 m3 mounted on a CAD4 diffractometer ꢀ/1.66q
mode with ꢀ scan width=0.80+0.34 tan q, ꢀ scan
speed 1.3–5.5° min−1, graphite-monochromated Mo–
Ka radiation. Of 6529 reflections collected, 6324 were
independent. „-Scan absorption correction (max. and
min. transmission: 99.95 and 73.98) giving 1517 with
I\2|(I). q range for data collection: 1.12–24.97°,
index ranges: −195h518, 05k514, 05l522. The
structure was solved by direct methods [31] (most
atoms) followed by difference Fourier synthesis and
refined by full-matrix least-squares on F2, using the
SHELXL-93 program [30] with all non-hydrogen atoms

M. Arroyo et al. / Journal of Organometallic Chemistry 599 (2000) 170–177
177
anisotropic. The weighting scheme w=[s2(Fo2)+
(0.0338P)2+0.00P]−1 where P=(Max[Fo2]+2F2c)/3.
Final R indices with I\2s(I): R1=0.0478, wR2=
0.0793, and R indices, with all data R1=0.1365, wR2=
0.0934.
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Crystallographic data (excluding structure factors)
for the reported structures have been deposited at the
Cambridge Crystallographic Data Centre with CCDC
nos. 101739, 101740 and 101741 for compounds 1a, 2a
and 3a, respectively.
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Acknowledgements
S.B. is grateful to UNAM for financial support and
USAI for diffractometer time. We are grateful to Dr.
Federico del Rio and Ing. L. Velasco (IQ) for help with
the instrumentation and to DGAPA-UNAM, Mexico
(IN121698), the European Union, CONACYT (25108E
and 27915E) and CSIC, Spain, for financial support.
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